The Role of the Substituent Pattern in Determining Selectivity in the Preparation of Tricarbonyl(η5-cyclohexadienyl)iron(1+) Salts by Acid-Catalyzed Demethoxylation

The factors that determine the selectivity of the acid-catalysed dealkoxylation of unsymmetrically substituted tricarbonyl(η4-alkoxycyclohexa-1,3-diene)iron(0) complexes have been investigated. Regioselective demethoxylation of complexes with a variety of substitution patterns has indicated that the selectivity arises from differences in the stabilization of the reaction intermediates and transition states by the diene substituents on the π-bound ligand. The observed regioisomers correspond to the product of the most stabilized intermediate pathway, rather than the product of minimum rearrangement. The reactions have been shown to proceed under kinetic control.